TWI648087B - Desulfurization material, purification column using the same, and pretreatment method for organic matter analysis - Google Patents

Abstract

As for a sulfur removal material which is cheaper than silver nitrate silicone and has a high sulfur removal effect, the present invention uses a sulfur removal material composed of a mixture of inorganic particles and an inorganic filler, and at least a part of the surface of the inorganic particles has a reaction with sulfur. Sexual metal. In addition, a purification column using the desulfurizing material is used for processing before organic substance analysis.

Description

Desulfurization material, purification column using the same, and pretreatment method for organic matter analysis Field of invention

The present invention relates to a sulfur-removing material which is applicable to pre-analytical treatment of organic substances such as residual organic pollutants, and a purification column and a pre-analytical treatment method using the same.

Background of the invention

When performing qualitative and quantitative analysis of residual organic pollutants (Persistent Organic Pollutants, POPs) such as dioxins or polychlorinated biphenyls (PCBs) contained in drainage, exhaust, soil, etc., the obstacles in the samples are usually removed in advance. The work of analyzing components is performed as a pre-processing to improve the accuracy of analysis.

Specifically, the sample is extracted with toluene, hexane, and the like, and purification of the extract is performed using, for example, a multi-layered silica gel column or the like. For a column packing material for removing sulfur in the sample, generally, such as JIS is used. The silver nitrate silicone described in K0311 (Measurement method for dioxins in exhaust gas) (for example, Patent Documents 1 and 2).

Silver nitrate silicone can effectively achieve sulfur removal by forming a complex with sulfur, but it has the problem of being time-consuming and expensive to manufacture. In contrast, cheaper, Although there is a demand for desulfurization materials with high desulfurization effect, the status quo is still unable to obtain desulfurization materials that meet these requirements.

Patent Document 3 related thereto discloses that in order to selectively absorb a specific component of a sample mixture in a preliminary stage of separation or analysis by chromatographic analysis, the first particles made of the first substance and the second particles are used. The mixture of the second particles is used as a separation medium. The first substance is silicon dioxide, organic polymers, silicic polymers, graphite, etc., which have been used in chromatographic columns. The first substance has a high thermal conductivity of silver, copper, aluminum, other metals, diamonds, carbon allotrope, and ceramics such as alumina.

However, in the separation medium described in Patent Document 3, the chromatographic separation method and the like performed under a very high pressure are mainly aimed at improving the separation efficiency by increasing the thermal conductivity of the separation medium, and before the analysis is performed. The removal of sulfur does not matter. The selection range of the first and second substances constituting each of the particles is extremely wide, and the blending amount of the second particles is preferably at least 1 to 25% of the total of the two, and about 10% is the most preferable.

Advance technical literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2002-40007

Patent Document 2: Japanese Patent Laid-Open No. 2002-122577

Patent Document 3: Japanese Patent Publication No. 2010-527003

Summary of invention

The present invention has been made in view of the above, and its purpose is to provide a desulfurization material which is cheaper than silver nitrate silicone and has a high desulfurization effect. Another object is to provide a purification column using the desulfurizing material and a method for pre-analyzing organic substances.

The sulfur-removing material of the present invention is used to remove sulfur in a liquid, and is composed of a mixture of inorganic particles and an inorganic filler. The inorganic particles have a metal reactive with sulfur on at least a part of the surface.

Among the above sulfur-removing materials, one or two or more metals selected from copper, silver, and iron can be used as the metal reactive with sulfur.

As the inorganic particles, copper particles whose surfaces are at least partially covered with silver can be used.

The specific surface area of the inorganic particles is preferably 0.2 m ² / g or more.

In addition, the inorganic particles are preferably dendritic or lumpy with irregularities on the surface.

The size of the inorganic particles should preferably be between 1 and 200 μm .

As said inorganic filler, 1 type, or 2 or more types selected from the group which consists of a silica gel, an alumina, a sea sand, and a glass bead can be used.

The size of the inorganic filler should preferably be an average particle size of 60 to 200 μm .

In the mixture of the inorganic particles and the inorganic filler, the blending ratio of the inorganic particles is preferably within a range of 0.1 to 50% by mass.

The purification column of the present invention is set to contain the sulfur removal material of the present invention described above.

The pre-treatment method for organic substance analysis of the present invention is a method for performing sulfur removal using the sulfur-removing material of the present invention.

The sulfur-removing material of the present invention can be cheaper to manufacture than silver nitrate silicon gel and has high sulfur-removing ability. Therefore, by using the sulfur-removing material of the present invention, the cost of pretreatment of analyzing organic substances such as residual organic pollutants can be reduced, and the accuracy or efficiency of the analysis can be further improved.

In addition, the sulfur-removing material of the present invention not only removes sulfur, but also removes polycyclic aromatic hydrocarbons (PAHs) or unsaturated hydrocarbons, and the ability to hinder the analysis of components is also at least the same as that of silver nitrate silicone.

Therefore, by using the desulfurization material of the present invention and the desulfurization method using the same, it is possible to carry out drainage, exhaust gas, and residual organic pollutants such as PCBs contained in dioxins and PCBs, which are cheaper and more accurate than in the past. Analysis.

A‧‧‧Multilayer Silicone Tubing

1‧‧‧ copper powder or copper sheet

2‧‧‧ sodium sulfate

3‧‧‧ desulfurization material

4, 7, 9‧‧‧ Silicone

5‧‧‧22% silicone sulfate

6‧‧‧44% silicone sulfate

8‧‧‧2% potassium hydroxide silicone

10‧‧‧ sodium sulfate

11‧‧‧Quartz Cotton

a‧‧‧ from the peak of polycyclic aromatic hydrocarbons

b‧‧‧ from the peak of unsaturated hydrocarbon

FIG. 1 is a schematic cross-sectional view showing the outline of a multilayer silicone tubing string.

Fig. 2 is a chromatogram showing the results of gas chromatography mass spectrometry (GC-MS) on each of the following samples: (1) a crude extract of the exhaust gas sample (before purification treatment); (2) the implementation of The treatment liquid obtained by purifying the crude extract of the exhaust gas sample of the desulfurization material of Example 1; (3) the treatment liquid obtained by purifying the crude extract of the exhaust gas sample using silver nitrate silicon gel.

Forms used to implement the invention

Hereinafter, embodiments of the present invention will be described more specifically.

As described above, the desulfurizing material of the present invention is composed of a mixture of inorganic particles and an inorganic filler, and the inorganic particles have a metal reactive with sulfur on at least a part of the surface.

First, the inorganic particles are not particularly limited as long as they have a metal reactive with sulfur on at least a part of the surface. Therefore, for example, metal particles composed of only one kind of metal having reactivity with sulfur may be used as the entire particle, or inorganic particles having a metal having reactivity with sulfur or an inorganic substance other than the metal particles may be used. A nucleus, and a part or all of the surface of the nucleus is coated with a metal having reactivity with sulfur.

The type of the metal having reactivity with sulfur is not particularly limited, and examples thereof include copper, silver, iron, lead, zinc, magnesium, sodium, and potassium, but from the viewpoint of reactivity with sulfur and cost balance Look, especially copper and silver.

The method for coating part or all of the surface of the inorganic substance that becomes a core with a metal having reactivity with sulfur is not particularly limited, and examples thereof include a method using electroless plating, a method using plating, vacuum evaporation, ionization, and the like. Methods such as plating, ion sputtering, and mechanochemical methods, but from the viewpoint of the ease of manufacturing the metal coating, the method using electroless plating is preferred.

The shape of the above-mentioned inorganic particles is not particularly limited, but in order to improve the sulfur removal ability, a shape having a large surface area is preferred. Therefore, compared with a near-spherical orb, it should be a dendritic shape, or a generally called "potato shape" with a bumpy surface on the surface, or a scaly shape.

If comprehensive consideration is taken to make the shape or cost of a large surface area as described above, copper particles are used as the core for inorganic particles, and The silver-coated copper particles whose surface is at least partially covered with silver are particularly preferred. By coating with silver, the oxidation resistance of copper particles can be improved. The amount of coating with silver is not particularly limited, and may be, for example, 1 to 20% by mass.

These inorganic particles may be used singly or as a mixture of two or more.

The size of the above-mentioned inorganic particles is not limited. However, considering the desulfurization ability and ease of operation, the average particle diameter is preferably 1 to 200 μm , and preferably 2 to 30 μm .

The specific surface area of the inorganic particles is not limited. However, in consideration of sulfur removal ability and the like, it is preferably 0.2 m ² / g or more, and more preferably 0.3 m ² / g or more.

Next, the inorganic filler used in the present invention is a particle that plays a role of keeping the above-mentioned inorganic particles at a proper interval from each other in an internal space such as a pipe column, and does not need to have a sulfur removal capability. For the above purpose, when the inorganic filler is mixed with the above-mentioned inorganic particles and filled in a column or the like under atmospheric pressure, the inorganic filler is preferably in a state where the mixed state with the inorganic particles can be stably maintained, and an organic solvent such as hexane can be used. Particles that pass through at an appropriate speed.

The type of the inorganic filler is not particularly limited, and examples thereof include silicone, alumina, sea sand, and glass beads. One of these inorganic fillers may be used alone, or a mixture of two or more of them may be used.

From the viewpoint of desulfurization ability and ease of operation, the size of the inorganic filler should preferably be an average particle diameter of 5 to 600 μm , and more preferably 60 to 200 μm .

The sulfur-removing material of the present invention can be obtained by mixing the above-mentioned inorganic particles and an inorganic filler. The means for mixing is not particularly limited, and a well-known stirring means can be appropriately used.

In the above-mentioned mixture of the inorganic particles and the inorganic filler, the mixing ratio of the inorganic particles is preferably in the range of 0.1 to 50% by mass, and more preferably in the range of 5 to 10% by mass, from the viewpoint of excellent sulfur removal ability.

The purification column of the present invention is a column containing the above-mentioned desulfurizing material of the present invention. The specific structure is not particularly limited, and may be, for example, described later. In the conventional multi-layered silicone tube column composed of a silicon layer and a silver nitrate silicon layer, etc., a layer filled with a desulfurizing material of the present invention is used instead of the silver nitrate silicon rubber. In terms of use, for example, it is possible to use a string for pretreatment of organic substances such as dioxin.

The method for pre-analyzing the organic matter of the present invention is a method for removing sulfur using the sulfur-removing material of the present invention. The specific method is not limited, and it can be made into, for example, the above-mentioned multi-layered silica gel column filled with the sulfur-removing material of the present invention instead of silver nitrate silica gel. A solvent extraction method to purify sulfur.

FIG. 1 is a schematic diagram showing an example of a multi-layer silicone tubing column used for processing before the analysis of organic substances. As shown in the figure, the multilayer silicone tube column has laminated silicon and other filling materials. In this example, the following layers are shown: Symbol 1 is copper powder or copper chip, and symbol 2 is sodium sulfate. Symbols 4, 7, and 9 are silicone rubber, symbol 5 is 22% sulfuric acid silicone rubber, symbol 6 is 44% sulfuric acid silicon rubber, symbol 8 is 2% potassium hydroxide silicon rubber, and symbol 10 is sulfur Sodium, symbol 11 is quartz wool. The layer shown by the symbol 3 is filled with the sulfur-removing material of the present invention instead of the conventional silver nitrate silicone rubber, and the sample liquid is passed through the column by the same method (under atmospheric pressure and room temperature), thereby removing sulfur.

The amount of the sulfur-removing material used in the present invention is not particularly limited. However, in order to obtain a sufficient sulfur-removing effect, in the case of using a column with an inner diameter of 10 to 15 mm and flowing down at a flow rate of about 2.5 ml / min, The thickness of the layer of sulfur material should be more than 20mm. If the processing capacity and cost are considered, it is better to be 20 ~ 30mm.

Examples

Examples of the present invention are shown below, but the present invention is not limited to the following examples. In addition, the following blending ratios and the like are mass standards unless otherwise specified.

1. Manufacturing of desulfurization materials

In the example, 20 g of Kanto Chemical Silicone 60N (Cat. No. 37565-79) and 1.4 g of various inorganic particles (silver-coated copper powder) shown in Table 1 were used, and a mixer (Automatic Mixer S-100 manufactured by TIETECH) was used for vibration. mixing. In the comparative example, silver nitrate silicone (silver content 6.5% by mass) was used.

In addition, the average particle diameter and specific surface area of the silver-coated copper powder were measured using a laser diffraction and diffusion type particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., MT3300EXII).

2. Evaluation of sulfur removal ability in hexane solution

To 0.8 g of the mixture in the example and 0.8 g of the silver nitrate silicone in the comparative example, 20 ml of a 3 mg / ml sulfur hexane solution was mixed, and stirred for 15 minutes. Of Then, the unreacted sulfur in the hexane solution was quantified by fluorescence X-ray analysis (Fundamental parameter method), and the sulfur sulfuric acid processing capacity (mg / g) of each 1 g of the mixture of the example and the comparative example was calculated. ). The results are shown in Table 1.

3. Evaluation of maximum recovery rate for dioxin removal

Using the sulfur-removing material of Example 1, the maximum recovery rate of dioxin removal was evaluated by JIS K0311 ("Calculation of the maximum recovery rate of 7.6.1 removal"). The results are shown in Table 2.

As shown in Table 1, the sulfur-removing materials of Examples 1 to 4 exhibited higher sulfur-handling capabilities than the silver nitrate silicone of the comparative example. It can also be seen that, as shown in Table 2, in the maximum recovery rate of dioxin removal, they fully meet the 50 ~ 120% stipulated by JIS K0311. The sulfur removal material of the present invention is cheaper and has a sulfur removal effect equal to or higher than that of silver nitrate silicone.

4.Removal ability of polycyclic aromatic hydrocarbons and unsaturated hydrocarbons in exhaust gas evaluation of

The 15 samples of the exhaust gas from the incinerator were collected and extracted according to JIS K0311, and the sample was randomly fractionated and mixed from the sample to be used as a crude extraction liquid sample for the exhaust gas sample. Chromatographic Mass Analysis (GC-MS). The obtained chromatogram is shown in Fig. 2 (1). The horizontal axis of the chromatogram shows the retention time (RT, minutes), the peaks in the part shown in (a) are from polycyclic aromatic hydrocarbons, and the peaks in the part shown in (b) are from unsaturated hydrocarbons.

<Gas Chromatography Mass Analysis (GC-MS) Device>

GC: 7890A by Agilent Technologies

MS: JMS-Q1050GC by JEOL

<GC measurement conditions>

Carrier gas: He

Note entry conditions: Splitless mode

Note inlet temperature conditions: 280 ° C

Oven temperature conditions: After initially holding at 150 ° C for 1 minute, the temperature was increased at a temperature increase rate of 20 ° C / min, and held at 320 ° C for 10 minutes. The maximum temperature at 320 ° C is 0.1 minutes.

<MS measurement conditions>

Ionization method: EI method

Free current: 70μA

Free energy: 70eV

Detector voltage: -1000V

Ion source temperature: 280 ° C

GCITF temperature: 280 ° C

The column (inner diameter: 13 mm) was filled with the sulfur-removing material of Example 1 or the silver nitrate silicon gel of the comparative example (filling height: 3 cm), and the crude extraction liquid sample of the exhaust gas sample was purified under the stream. After the treatment, GC-MS analysis was performed under the same conditions as above. The processing result using the sulfur-removing material of Example 1 is shown in (2) of FIG. 2, and the processing result using the silver nitrate silicone of the comparative example is shown in (3).

It can be seen from the comparison of these chromatograms that the sulfur-removing material of the present invention is equivalent to or more than silver nitrate silicone even in its ability to remove polycyclic aromatic hydrocarbons or monocyclic aromatic hydrocarbons, which hinders analysis components.

Claims (8)

A purification column contains a desulfurizing material for removing sulfur in a liquid. The desulfurizing material is composed of a mixture of inorganic particles and an inorganic filler, and the inorganic particles have a reactive property with sulfur on at least a part of the surface. metal. According to the purification column of claim 1, wherein the metal reactive with sulfur is one or two or more selected from copper, silver, and iron. The purification column of claim 1, wherein at least a part of the aforementioned inorganic particles are copper particles whose surface is covered with silver. The purification column of claim 1, wherein the specific surface area of the inorganic particles is 0.2 m ² / g or more. An organic substance pre-treatment method, characterized in that: sulfur removal is performed using a sulfur removal material for removing sulfur in a liquid, the sulfur removal material is composed of a mixture of inorganic particles and an inorganic filler, and the inorganic particles are At least a portion of the surface has a metal reactive with sulfur. For example, the pretreatment method of organic matter analysis according to claim 1, wherein the metal reactive with sulfur is one or more selected from copper, silver, and iron. The method for processing organic matter before analysis according to claim 1, wherein the inorganic particles are copper particles whose surfaces are at least partially covered with silver. For example, the method for processing organic matter before analysis according to claim 1, wherein the specific surface area of the inorganic particles is 0.2 m ² / g or more.